US2400808A - Preparation of aqueous dispersions of vinyl chloride polymers - Google Patents

Preparation of aqueous dispersions of vinyl chloride polymers Download PDF

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Publication number
US2400808A
US2400808A US503266A US50326643A US2400808A US 2400808 A US2400808 A US 2400808A US 503266 A US503266 A US 503266A US 50326643 A US50326643 A US 50326643A US 2400808 A US2400808 A US 2400808A
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vinyl chloride
groups
polymer
free
parts
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US503266A
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Edward R Burns
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DISPERSIONS PROCESS Inc
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DISPERSIONS PROCESS Inc
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
    • C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
    • C08J3/05—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media from solid polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
    • C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L27/04—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
    • C08L27/06—Homopolymers or copolymers of vinyl chloride
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2327/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
    • C08J2327/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
    • C08J2327/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
    • C08J2327/06—Homopolymers or copolymers of vinyl chloride
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L89/00—Compositions of proteins; Compositions of derivatives thereof
    • C08L89/005—Casein

Definitions

  • Vinyl chloride polymers which are free from OH groups are not capable of being dispersed in an aqueous medium by the conventional procedure of mixing into the polymer a plasticizing agent and a hydrophilic colloidal dispersing agent, and adding water to the plasticized mass, as in an internal mixer, until an inversion of phase takes place.
  • the batch breaks up into small pieces with the dispersing agent, such as soap, running out of the broken batch.
  • the vinyl chloride polymer which is free trom OH groups another vinyl chloride polymer which contains OH groups
  • plasticizer and hydrophilic colloidal dispersing agent after which on addition of water to the plasticized mass with the usual kneading and stretching of the mass as in an internal mixer, such as a Werner 8a Pfleiderer mixer, an inversion of phase takes place and the polymers disperse in the aqueous medium.
  • the plasticizer may be any of the conventional plasticizers for vinyl polymers and the hydrophilic colloidal dispersing agent may be a conventional dispersing agent, such as a protein, for example solubilized casein, or soap.
  • the vinyl chloride polymer which contains OH groups may be either a polyvinyl chloride or a vinyl chloride-vinyl acetate copolymer and either of such vinyl chloride polymers may be added to the vinyl chloride polymer which it is desired to disperse in the aqueous medium.
  • the amount to be added of the vinyl chlo ride polymer which contains OH groups, and the degree of hydrolysis of such vinyl chloride polymer may be varied as desired. 10 to 25 parts of a vinyl chloride polymer containing as little as 3% of the ester groups hydrolyzed to OH groups, will readily permit the dispersion in water of a vinyl chloride polymer which is free from OH groups.
  • the following examples are illustrative of the invention:
  • Example I parts (all parts herein are by weight) of a commercial powdered vinyl chloride-vinyl acetate copolymer which is free from OH groups (Vinylite VYNW) were introduced into a Werner and Pileiderer mixer and to the same was added with constant mixing 10 parts of a commercial vinyl chloride-vinyl acetate copolymer which conf tained about 3% of OH groups based on the total ester groups (Vinylite VMCH).
  • 50 parts of a commercial plasticizer dibutoxy-ethyl phthalate and 3 parts of zinc stearate were mixed with the vinyl chloride polymers followed by 20 parts of casein and 1.4 parts of sodium fluoride in a form of a 50% aqueous suspension.
  • Example II In this case V5 parts of a commercial powdered. vinyl chloride-vinyl acetate copolymer which is free from OH groups (Vinylite VYNS) were introduced into a Werner and Pfleiderer mixer and there was added 25 parts of Vinylite phase took place and the polymer particles become dispersed in the aqueous medium, after which further water was added to a 50% solids concentration.
  • the Vinylite VYNS could not -be dispersed without the addition of the Vinylite VMCH containing the OH groups.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Dispersion Chemistry (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Description

Patented May 21, 1946 PREPARATION OF AQUEOUS DISPERSIONS" F VINYLCHLQRIDE POLYMERS Edward R. Burns, Cheshire, Conn., assignor, by mesne assignments, to Dispersions Process, Inc., New York, N. Y., a corporation of Delaware No Drawing. Application September 21, 1943, Serial No. 503,266
(Cl.260-32) i c i Claims.
This invention relates to the preparation of aqueous dispersions of vinyl chloride polymers, for example, polymerized vinyl chloride, and vinyl chloride-vinyl acetate copolymers, and more particularly to the preparation of aqueous dispersions of vinyl chloride polymers which are free from OH groups.
Vinyl chloride polymers which are free from OH groups are not capable of being dispersed in an aqueous medium by the conventional procedure of mixing into the polymer a plasticizing agent and a hydrophilic colloidal dispersing agent, and adding water to the plasticized mass, as in an internal mixer, until an inversion of phase takes place. On addition of water to such a plasticized mass to the point where inversion of phase should ordinarily take place, the batch breaks up into small pieces with the dispersing agent, such as soap, running out of the broken batch.
According to the present invention, I have been able to prepare an aqueous dispersion of vinyl chloride polymer, such as polyvinyl chloride, and vinyl chloride-vinyl acetate copolymer, which are free from OH groups.
In carrying out the invention, there is mixed with the vinyl chloride polymer which is free trom OH groups, another vinyl chloride polymer which contains OH groups, together with the usual plasticizer and hydrophilic colloidal dispersing agent, after which on addition of water to the plasticized mass with the usual kneading and stretching of the mass as in an internal mixer, such as a Werner 8a Pfleiderer mixer, an inversion of phase takes place and the polymers disperse in the aqueous medium. The plasticizer may be any of the conventional plasticizers for vinyl polymers and the hydrophilic colloidal dispersing agent may be a conventional dispersing agent, such as a protein, for example solubilized casein, or soap. The vinyl chloride polymer which contains OH groups may be either a polyvinyl chloride or a vinyl chloride-vinyl acetate copolymer and either of such vinyl chloride polymers may be added to the vinyl chloride polymer which it is desired to disperse in the aqueous medium. The amount to be added of the vinyl chlo ride polymer which contains OH groups, and the degree of hydrolysis of such vinyl chloride polymer may be varied as desired. 10 to 25 parts of a vinyl chloride polymer containing as little as 3% of the ester groups hydrolyzed to OH groups, will readily permit the dispersion in water of a vinyl chloride polymer which is free from OH groups. The following examples are illustrative of the invention:
Example I parts (all parts herein are by weight) of a commercial powdered vinyl chloride-vinyl acetate copolymer which is free from OH groups (Vinylite VYNW) were introduced into a Werner and Pileiderer mixer and to the same was added with constant mixing 10 parts of a commercial vinyl chloride-vinyl acetate copolymer which conf tained about 3% of OH groups based on the total ester groups (Vinylite VMCH). 50 parts of a commercial plasticizer dibutoxy-ethyl phthalate and 3 parts of zinc stearate were mixed with the vinyl chloride polymers followed by 20 parts of casein and 1.4 parts of sodium fluoride in a form of a 50% aqueous suspension. 10 parts of water were then mixed in, followed by 1.5 parts of triethanolamine and 15 parts of 26 B. ammonia. Water was slowly added to the thus plasticized mass in the internal mixer with kneading and stretching of the mass, until an inversion of phase took place and the polymer particles became dispersed in the aqueous medium. Further water was added to a 45% solids dispersion. Without the addition of the 10 parts of Vinylite VMCH, the batch broke up into small pieces without dispersing the polymer particles.
Example II In this case V5 parts of a commercial powdered. vinyl chloride-vinyl acetate copolymer which is free from OH groups (Vinylite VYNS) were introduced into a Werner and Pfleiderer mixer and there was added 25 parts of Vinylite phase took place and the polymer particles become dispersed in the aqueous medium, after which further water was added to a 50% solids concentration. The Vinylite VYNS could not -be dispersed without the addition of the Vinylite VMCH containing the OH groups.
Example III In this case a commercial polyvinyl chloride which was free from OH groups (Koroseal) could not be dispersed on casein following the procedure in Example I. The addition of '20 parts of Vinylite VMCH" to 80 parts of the Koroseal, permitted the Koroseal to be readily dispersed on casein, following the procedure shown in Example I.
In View of the many changes and modifications that may be made without departing from the principles underlying the invention, referones should be made to the appended claims for an understanding of the scope of the protection afforded the invention.
Having thus described my invention, what I claim and desire to protect by Letters Patent is:
l. The process of preparing an aqueous dispersion of a vinyl chloride polymer which is free from OH groups comprising mixing with said polymer a vinyl chloride polymer which contains OH groups, a plasticizer and a hydrophilio colloidal dispersing agent, and adding water to the plasticized mass until an inversion of phase takes place and the polymer particles become dispersed in the aqueous medium.
The process of preparing an aqueous dispersion of a vinyl chloride polymer which is free from OH groups comprising mixing with said polymer, a vinyl chloride polymer which contains OH groups, a plasticizer and a hydrophilic colloidal dispersing agent, and adding water to the plasticized mass in an internal mixer with kneading and stretching of the mass until an inversion oi. phase takes place and the polymer particles become dispersed in the aqueous medium.
3. The process of preparing an aqueous dispersion of a vinyl chloride-vinyl acetate copolymer which is free firom OH groups comprising mixing with said copolymer a vinyl chloride polymer which contains OH groups, a plasticizer and a hydro colloidal dispersing agent, and plasticized mass until an rsion or phase takes place and the polymer icles hecome dispersed in the aqueous meurn,
d. The process or" preparing an aqueous dispersion of a vinyl chloride-vinyl acetate copolymer which is free from OH groups comprising mixing with said copolymer a. vinyl chloride-vinyl acetate copolymer which contains OH groups, a plasticizer and a hydrophilic colloidal dispersing agent, and adding water to the plasticized mass in an internal mixer with kneading andstretching of the mass until an inversion of phase takes place and the polymer particles become dispersed in the aqueous medium.
5. The process of preparing an aqueous dispersion of a vinyl chloride polymer which is free from OH groups, comprising adding water to a plasticized mass containing said vinyl chloride polymer, a vinyl chloride polymer which contains 01-]: groups and a hydrophilic colloidal dispersing agent, until an inversion of phase takes place and the copolymers become dispersed in the aqueous medium.
6. The process of preparing an aqueous dispersion of polyvinyl chloride, which is free from OH groups, comprising adding water in an internal mixer to a-plasticized mass containing said polyvinyl chloride, a vinyl chloride polymer which contains OH groups and a hydrophilic col-- loidal dispersing agent, until an inversion of phase takes place and the polymer particles become dispersed in the aqueous medium.
"7. The process of preparing an aqueous dispersion of a vinyl chloride-vinyl acetate copolymer which is free from OH groups, comprising adding water to a plasticized mass containing said copolymer, a vinyl chloride polymer which contains OH groups and a hydrophilic colloidal dispersing agent, until an inversion of phase takes place and the polymer particles become dispersed in the aqueous medium.
8. The process of preparing an aqueous dispersion of a vinyl chloride-vinyl acetate copolymer which is free from OH groups, comprising adding water in an internal mixer to a plasticized mass containing said copolymer, a vinyl chloridevinyl acetate copolymer which contains OH groups and a hydrophilic colloidal dispersing agent, until an inversion of phase takes place and the copolymers become dispersed in the aqueous medium.
9. The product oi the process of claim 5.
10. The product 01 the process of claim 7.
EDWARDRBURNS.
US503266A 1943-09-21 1943-09-21 Preparation of aqueous dispersions of vinyl chloride polymers Expired - Lifetime US2400808A (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2511113A (en) * 1947-05-16 1950-06-13 Stein Hall & Co Inc Pigment binders
US2512726A (en) * 1944-09-20 1950-06-27 Union Carbide & Carbon Corp Composition of vinyl chlorideacetate-alcohol copolymer
US2514191A (en) * 1946-06-29 1950-07-04 Firestone Tire & Rubber Co Antisticking treatment of vinyl resins
US2958668A (en) * 1956-04-09 1960-11-01 Us Rubber Co Method of making vinyl chloridedialkyl maleate copolymer latex

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2512726A (en) * 1944-09-20 1950-06-27 Union Carbide & Carbon Corp Composition of vinyl chlorideacetate-alcohol copolymer
US2514191A (en) * 1946-06-29 1950-07-04 Firestone Tire & Rubber Co Antisticking treatment of vinyl resins
US2511113A (en) * 1947-05-16 1950-06-13 Stein Hall & Co Inc Pigment binders
US2958668A (en) * 1956-04-09 1960-11-01 Us Rubber Co Method of making vinyl chloridedialkyl maleate copolymer latex

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